200521203 (1) 九、發明說明 【發明所屬之技術領域】 本發明係關於：至少主要由聚乙烯（P E )或 P P )構成的一種額外包含抗粘連劑之塑料膜材， 產該膜材時作爲抗粘連劑之用途，生產該膜材用 生產該膜材所需抗粘連劑母料的方法，含有該種 的PP或 PE樹脂，以及生產這種樹脂的方法。 【先前技術】 ί几粘連劑是膜材生產中一種常用而又有效的 以致於幾乎所有的膜材中都含有。如圖1所示， 產中，當塑料原料1 2通過滾筒組1 4時，它依然 受到擠壓，然後才被纏到卷筒1 4 a上。如圖2所 卷的膜材16在滾筒壓力、捲筒張力和大氣壓力 下’膜材1 6就容易粘在一起，很難分開。我們 S勁打開包裝雜貨之透明塑料袋、或者試圖分開 膜或覆蓋膜、或者捲上或者拉出薄膜，遇到的就 ffi難。尋求一種高效率高透明度的抗粘連劑是長 材生產行業的夙願。 膜層之間的粘合或者粘連是包括 PE和PP 合物材料所固有的一個特徵。因此，爲了降低膜 粘連，薄膜生產中加入了抗粘連劑。 從工作原理來看，抗粘連劑主要分爲微粒型 (即：抗粘連劑由膜材內部遷移到膜材表面）。 聚丙烯（ 沸石在生 的母料， 抗粘連劑 添加劑， 在膜材生 是熱的並 示，當回 三者作用 平時經常 單層包裝 是這樣的 期以來膜 等眾多聚 層之間的 和遷移型 -4- 200521203 (2) 對於微粒型抗粘連劑，請參見圖3、圖4。微粒 加入聚合體中，故膜材1 6的表面出現了凸起的小點 些凸起的抗粘連劑微粒降低了膜材粘力，使膜材16 於粘在一起。具體而言，即使膜材1 6仍然受大氣壓 影響，在顯微鏡下才能看見的膜材1 6的粗糙表面同 空氣能進入各個層間，從而降低層間粘合。 能用於微粒型抗粘連劑的微粒有多種類型，但在 和成本上卻迥然不同。最廉價的莫過於天然滑石或二 矽（Si02 )(後者如圖1 1所示）。但它們不僅透明 低而且純度也差。 現在，最高透明度、最高抗粘力的微粒型抗粘連 用的是低密度合成二氧化矽，如圖1 2所示。 至於遷移型抗粘連劑，它會遷移到膜材1 6的表 尤其是在高溫狀態下。這就避免了膜材粘在生產、包 加工設備的滾筒上。如圖5所示，抗粘連劑從膜層] 徙到膜材表面2 8，從而達成抗粘連的效果。遷移型 連劑不僅使薄膜便於分開而且還很滑。 此外，還可以把抗粘連劑分爲有機類（如醯胺蠟 無機類（如滑石、天然的和合成的二氧化矽）。 隨著塑料工業的發展，市場繼續期望更高透明度 料袋。透明度不僅受基本原料配合比例和原料本身不 學結構的影響，還受所使用抗粘連劑類型的影響。目 有微粒型抗粘連劑對塑料袋的透明度都有負面影響， 最普遍的就是在薄膜中產生的霧狀效應。這霧度通常 20被 。這 不至 力的 樣使 品質 氧化 度較 劑使 面， 裝和 [6遷 抗粘 )和 的塑 同化 前所 其中 取決 ->5- 200521203 (3) 於抗粘連劑的如下特徵： a·抗粘連劑純度：天然礦物的微粒型抗粘連劑通常 都沒有人工合成抗粘連劑的純度高；所以，人工合成抗粘 連劑能使薄膜有更高的透明度； b ·抗粘連劑的折射率：如果兩種不同材料具有非常 相似的折射率，那麼當光線通過它們時，光在塑料薄膜中 的損失就能最小化。相反，如果兩種不同材料具有相差較 大的折射率，光在通過二者後就有非常明顯的損失。如圖 6、7所示，當光線30從空氣32進入塑料薄膜34 (如PE 或者PP )時，產生了第一次折射。隨後，當光線3 0進入 薄膜3 4的抗粘連劑微粒3 6時，產生了第二次折射。折射 度取決於塑料材料和抗粘連劑的折射率，如下公式所述： sina/sir^ =抗粘連劑微粒折射率/基本塑料原料折射率 當光線3 0離開微粒3 6並再進入薄膜3 4時，光線再 次發生折射。可以看出，如果抗粘連劑微粒折射率和製造 薄膜3 4的基本原料折射率越相近，光線3 0發生的偏離就 越小，光線就損失得越少。 天然滑石和二氧化矽的折射率分別是1.57和1.46, 而P E和P P的折射率卻分別是1 · 4 9和1 · 5 0。由於折射率 不同，通過天然滑石和二氧化矽的光線會大量減少，塑料 袋的-尤其是以這兩種微粒爲抗粘連劑的PE和 PP塑料 袋的-透明度也因此大受影響。 無機微粒類抗粘連劑的效能取決於以下因素： i.微粒的大小：微粒越大，膜材表面越粗糙； -6 - 200521203 (4) i i.微粒的形態：與圓形微粒相比，無定形微粒使膜 材表面更粗糙； ϋί.所加入的抗粘連劑微粒總量：微粒越多，膜材表 面越粗糙； iv·微粒的被覆：當可從熔化的PE和pp材料中遷移 出來的化學物質（或者通過極性機制，或者通過其它某種 機制）覆蓋在微粒上，能幫助微粒突出在膜材表面上時， 表面的粗糙程度就會增強。 選用抗粘連劑時，還要考慮它的硬度。如圖8所示， 當包含抗粘連劑的塑料原料40流過機器基板42時（例如 ，在製造母料以供隨後製造塑料膜材之期間），抗粘連劑 微粒44會與基板42的表面46發生磨擦。例如，二氧化 石夕晶體的莫氏硬度 （Mohs Hardness)爲 7，而鑽石的莫 氏硬度爲1 〇。所以，使用如此硬的抗粘連劑會使與抗粘 連劑接觸之機器部件的磨損增大。關於這一點，我們還可 以發現由化學引力將初生粒子聚集在一起的次生粒子（如 圖9所示），結構非常緻密，堅硬，其形狀不能改變；而 由物理引力（範德瓦耳斯引力）凝聚在一起的球團結構粒 子（如圖1 〇所示）的結構卻較鬆散、柔軟，其形狀相對 容易改變。 【發明內容】 因此’本發明之一目標爲提供一種膜材，其內含有類 似天然ί母；τ'帛狀結構的微粒作爲抗粘連劑’能減少上述高剛 200521203 (5) 性抗粘連劑之缺點，或至少爲大眾提供一種有用的選擇。 根據本發明之第一方面，提供一種塑料膜材，包含（ a )聚乙烯（PE )或者聚丙烯（PP )，及（b )沸石抗粘 連劑。這種沸石抗粘連劑的次級粒子直徑實質上小於0.4 微米；由這種初始粒子形成的聚集體的大多數次級粒子的 直徑實質上小於0 · 4微米·，而且，上述大多數這種次級粒 子是線性鏈狀結構。 根據本發明之第二方面，提供在至少以聚乙烯（PE ) 或者聚丙烯（PP )爲主要原料的塑料膜材生產中以沸石作 爲抗粘連劑之用途，其中該沸石次級粒子直徑實質上小於 〇·4微米；由初始粒子形成的聚集體的大多數次級粒子的 直徑實質上小於0.4微米；而且，上述大多數這種次級粒 子是線性鏈狀結構。 根據本發明之第三方面提供一種生產塑料薄膜的母料 ’它包含（a )聚乙烯（PE )或者聚丙烯（PP )，及（b )沸石抗粘連劑。這種沸石抗粘連劑的次級粒子直徑實質 ±小於0 · 4微米；由初始粒子形成的聚集體的大多數次級 粒子的直徑實質上小於〇 . 4微米；而且，上述大多數這種 次級粒子是線性鏈狀結構。 根據本發明之第四方面，提供了 一種生產抗粘連母料 的方法，它包括在聚合過程中把作爲抗粘連劑之沸石加入 聚乙烯（PE )或者聚丙烯（PP )樹脂的步驟。這種沸石 抗粘連劑的初始粒子直徑實質上小於0.4微米；這種沸石 的次級粒子由上述初級粒子的聚集體構成；大多數上述次 -8- 200521203 (6) 級粒子的直徑實質上小於〇·4微米；而且，上述大多數這 種次級粒子是線性鏈狀結構。 根據本發明之第五方面，提出了 一種含有沸石作爲抗 粘連劑的聚乙燒（Ρ Ε )或聚丙烯（ρ ρ )樹脂，其中，所 述沸石的基本粒子的直徑實質上小於〇 4微米，次級粒子 是由上述基本粒子聚集而成的，並且大多數次級粒子的直 徑實質上小於0.4微米，同時，其中所述的大部分次級粒 子的結構是線性鏈形狀的。 根據本發明之第六方面，提出了一種生產聚乙烯（ΡΕ )或聚丙烯（ΡΡ )樹脂的方法，包括在聚合方法中向聚乙 烯（ΡΕ)或聚丙烯（ΡΡ)樹脂中添加沸石的步驟，其中 所述沸石的基本粒子的直徑實質上小於〇. 4微米，次級粒 子是由上述基本粒子聚集而成的，並且大多數次級粒子的 直徑實質上小於0 · 4微米，其中所述的大部分次級粒子的 結構是線性鏈形狀的。 【實施方式】 微粒型抗粘連劑的-尤其是無機類微粒型抗粘連劑的 -玻璃透明度和低霧度特性，是生產高透明度膜材所要求 的重要特徵。如上所述，ΡΕ和 ΡΡ的折射率分別爲1.49 和1 .5 0，所以，在生產高透明度的 ΡΕ和 ΡΡ膜材時，理 想的玻璃透明度無機類微粒型高效抗粘連劑的折射率應該 在1.49-1.50之間。這樣，當光線通過混有這種抗粘連劑 的ΡΕ或ΡΡ膜材時，它才能和原有入射方向和強度保持 -9- 200521203 (7) 高度的一致，從而使霧度最低。 根據發明者的理論，爲了生產出高透明度的合成 PE fP PP膜材，除了要求抗粘連劑折射率在1.49-1.50 之間外，它本身還應該具有如下一個或多個特徵： 1 ·抗粘連劑初級粒子的直徑小於0 · 4微米； 2 ·由抗粘連劑初級粒子聚集形成的次級粒子是線性 鏈狀結構； 3.大多數次級粒子的直徑小於可見光波長（0.4-0.7 微米）； 4 ·由這些次級粒子凝聚形成的三級粒子形態與天然 海綿相似，即三級粒子之間應該有許多間隙。 本發明者還認爲，要進一步增高膜材的玻璃透明度 ，一*方面，初級粒子應該具有圓而光滑的外形，即表面沒 有尖銳邊緣；另一方面，遷移性的化學物質對抗粘連劑作 表面預塗能增強產品的抗粘連功能。 根據以上理論，在做了很多篩選和實驗後，我們發現 德國DegussaAG公司生產和銷售的、以EXP5700-1命名 的一種特殊沸石能滿足以上各項要求。在P E和P P膜材 生產中，EXP 5 7 00- 1是一種尤其好的抗粘連劑。它既能保 δ登膜材有很局的透明度’又有其它很多優點。和其它沸石 一樣，ΕΧΡ5700-1的折射率是1.50(參見 Plastics Additives Handbook，Ed. Hans Zweifel, 5th Edition， Munich: Hanser，2000《塑料添加劑手冊》，Hans Zweifel 編，第五版，慕尼黑：漢莎，2000，ρ·588)。 -10- 200521203 (8)200521203 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to: an additional plastic film material containing an anti-blocking agent mainly composed of at least polyethylene (PE) or PP. Application of anti-blocking agent, method for producing anti-blocking agent masterbatch required for producing the film material, containing such PP or PE resin, and method for producing such resin. [Prior art] Several adhesives are commonly used and effective in the production of film materials, so that almost all film materials are contained. As shown in Figure 1, during production, when the plastic raw material 12 passes through the roller group 14, it is still squeezed, and then it is wound on the roll 14a. The film material 16 rolled as shown in Fig. 2 is easy to stick together and difficult to separate under the pressure of the drum, the tension of the roll and the atmospheric pressure. When we try to open the transparent plastic bag for packaging groceries, or try to separate the film or cover film, or roll or pull the film, it is difficult to meet. The search for an anti-blocking agent with high efficiency and transparency is the wish of the long product manufacturing industry. Adhesion or blocking between film layers is a characteristic inherent in materials including PE and PP compounds. Therefore, in order to reduce film blocking, anti-blocking agents are added to film production. From the working principle, anti-blocking agents are mainly divided into particulates (that is, anti-blocking agents migrate from the inside of the film to the surface of the film). Polypropylene (zeolite raw masterbatch, anti-blocking agent additive, is hot in the film and shows that when the three functions, usually single-layer packaging is such a period of time between the film and many other polymer layers and migration Type -4- 200521203 (2) For particulate anti-blocking agents, please refer to Figures 3 and 4. The micro-particles are added to the polymer, so the surface of the membrane material 16 has raised bumps and some raised anti-blocking agents. The particles reduce the adhesive force of the film material and make the film material 16 stick together. Specifically, even if the film material 16 is still affected by the atmospheric pressure, the rough surface of the film material 16 that can be seen under the microscope can enter the various layers with air. , Thereby reducing the interlayer adhesion. There are many types of particles that can be used for particle-type anti-blocking agents, but the cost is very different. The cheapest is natural talc or silicon dioxide (Si02) (the latter is shown in Figure 11) (Shown). But they are not only low in transparency but also poor in purity. At present, low-density synthetic silica is used for the particulate type anti-blocking with the highest transparency and the highest anti-blocking strength, as shown in Figure 12. As for the migration-type anti-blocking agent And it will migrate to The surface of the material 16 is especially at a high temperature. This prevents the film from sticking to the rollers of the production and packaging processing equipment. As shown in Figure 5, the anti-blocking agent migrates from the film layer to the surface of the film 28, So as to achieve anti-blocking effect. Migration-type linking agent not only makes the film easy to separate but also slippery. In addition, anti-blocking agents can also be divided into organic (such as ammonium wax inorganic (such as talc, natural and synthetic two) Silicon oxide). With the development of the plastics industry, the market continues to expect more transparent material bags. Transparency is not only affected by the proportion of basic materials and the non-learning structure of the materials themselves, but also by the type of anti-blocking agent used. There are particles Type anti-blocking agents have a negative impact on the transparency of plastic bags. The most common is the haze effect produced in the film. This haze is usually 20 coats. This is not enough to make the quality oxidation degree more than the surface of the agent. [6Qian anti-sticking] and plastic assimilation depends on what-> 5-200521203 (3) The following characteristics of anti-blocking agents: a. Anti-blocking agent purity: natural mineral particulate anti-blocking agents are usually not There are synthetic anti-blocking agents with high purity; therefore, synthetic anti-blocking agents can make the film have higher transparency; b · refractive index of anti-blocking agents: if two different materials have very similar refractive indexes, then when the light When passing through them, the loss of light in the plastic film can be minimized. On the contrary, if two different materials have refractive indexes with large differences, light will have a very significant loss after passing through the two. See Figures 6 and 7 It shows that when the light 30 enters the plastic film 34 (such as PE or PP) from the air 32, a first refraction occurs. Subsequently, when the light 30 enters the anti-blocking agent particles 36 of the film 34, a second Refraction. The degree of refraction depends on the refractive index of the plastic material and the anti-blocking agent, as described in the following formula: sina / sir ^ = anti-blocking agent particle refractive index / basic plastic raw material refractive index When the film 34 is thin, the light is refracted again. It can be seen that if the refractive index of the anti-blocking agent particles is closer to the refractive index of the basic raw material for manufacturing the thin film 34, the smaller the deviation of the light 30 is, the less the light is lost. The refractive indices of natural talc and silicon dioxide are 1.57 and 1.46, respectively, while the refractive indices of PE and PP are 1.49 and 1.50 respectively. Due to the different refractive index, the light passing through natural talc and silica will be greatly reduced, and the transparency of plastic bags-especially PE and PP plastic bags with these two particles as anti-blocking agents-will be greatly affected. The effectiveness of inorganic particulate anti-blocking agents depends on the following factors: i. The size of the particulates: the larger the particulates, the rougher the surface of the film; -6-200521203 (4) i. The shape of the particulates: compared with the Amorphous particles make the surface of the film more rough; ϋ. The total amount of anti-blocking agent particles added: the more particles, the rougher the surface of the film; iv. Coating of the particles: when it can be migrated from the molten PE and pp materials When the fine chemical substances (either through the polar mechanism or some other mechanism) cover the particles, they can help the particles to protrude on the surface of the film, and the surface roughness will increase. When choosing an anti-blocking agent, also consider its hardness. As shown in FIG. 8, when the plastic raw material 40 containing the anti-blocking agent flows through the machine substrate 42 (for example, during the production of a master batch for the subsequent manufacturing of a plastic film material), the anti-blocking agent particles 44 will be on the surface of the substrate 42 46 Friction occurred. For example, the Mohs Hardness of the spar crystal is 7 and the Mohs hardness of the diamond is 10. Therefore, the use of such a hard anti-blocking agent increases the wear of machine parts that come into contact with the anti-blocking agent. In this regard, we can also find that the secondary particles (primarily shown in Figure 9) that aggregate the primary particles together by chemical gravity have a very dense and hard structure, and their shape cannot be changed; and by physical gravity (Vandervalls Gravity) The structure of the pellet structure particles (shown in Figure 10) is relatively loose and soft, and its shape is relatively easy to change. [Summary of the Invention] Therefore, 'one of the objects of the present invention is to provide a film material containing a natural mother; τ' microstructure-like particles as an anti-blocking agent 'can reduce the above-mentioned high rigidity 200521203 (5) anti-blocking agent Disadvantages, or at least provide a useful option for the general public. According to a first aspect of the present invention, a plastic film material is provided, comprising (a) polyethylene (PE) or polypropylene (PP), and (b) a zeolite anti-blocking agent. The secondary particle diameter of this zeolitic anti-blocking agent is substantially less than 0.4 micrometers; most secondary particles of aggregates formed from such primary particles are substantially smaller than 0.4 micrometers, and most of the above-mentioned The secondary particles have a linear chain structure. According to a second aspect of the present invention, there is provided the use of zeolite as an anti-blocking agent in the production of plastic film materials using at least polyethylene (PE) or polypropylene (PP) as a main raw material, wherein the diameter of the secondary particles of the zeolite is substantially Less than 0.4 micrometers; most secondary particles of aggregates formed from primary particles have a diameter of substantially less than 0.4 micrometers; and most of the above-mentioned secondary particles have a linear chain structure. According to a third aspect of the present invention, a masterbatch for producing a plastic film is provided which comprises (a) polyethylene (PE) or polypropylene (PP), and (b) a zeolite anti-blocking agent. The secondary particle diameter of this zeolitic anti-blocking agent is substantially ± less than 0.4 microns; the diameter of most secondary particles of the aggregate formed by the primary particles is substantially less than 0.4 microns; The first-order particles have a linear chain structure. According to a fourth aspect of the present invention, there is provided a method for producing an anti-blocking masterbatch, comprising the step of adding zeolite as an anti-blocking agent to a polyethylene (PE) or polypropylene (PP) resin during the polymerization process. The primary particle diameter of this zeolitic anti-blocking agent is substantially smaller than 0.4 micrometers; the secondary particles of this zeolite are composed of aggregates of the above-mentioned primary particles; most of the above-mentioned sub-8-200521203 (6) grade particles have diameters substantially smaller than 0.4 micron; moreover, most of these secondary particles have a linear chain structure. According to a fifth aspect of the present invention, a polyethylene (PE) or polypropylene (ρ ρ) resin containing a zeolite as an anti-blocking agent is proposed, wherein the diameter of the elementary particles of the zeolite is substantially smaller than 0.4 μm The secondary particles are aggregated from the above-mentioned basic particles, and the diameter of most of the secondary particles is substantially smaller than 0.4 micrometers. At the same time, the structure of most of the secondary particles is linear chain shape. According to a sixth aspect of the present invention, a method for producing a polyethylene (PE) or polypropylene (PP) resin is provided, which includes the step of adding zeolite to the polyethylene (PE) or polypropylene (PP) resin in a polymerization method. Wherein the diameter of the primary particles of the zeolite is substantially smaller than 0.4 micrometers, the secondary particles are aggregated by the above-mentioned basic particles, and the diameter of most of the secondary particles is substantially smaller than 0.4 micrometers, wherein The structure of most of the secondary particles is linear chain shape. [Embodiment] The microparticle type anti-blocking agent-especially the inorganic microparticle type anti-blocking agent-glass transparency and low haze characteristics are important characteristics required for the production of high transparency films. As mentioned above, the refractive indices of PE and PP are 1.49 and 1.5 respectively. Therefore, when producing highly transparent PE and PP films, the refractive index of the ideal glass transparency inorganic particulate high-efficiency anti-blocking agent should be between Between 1.49-1.50. In this way, when the light passes through the PE or PP film mixed with this anti-blocking agent, it can keep the same height and direction as the original incident direction and intensity -9- 200521203 (7), so as to minimize the haze. According to the inventor's theory, in order to produce a highly transparent synthetic PE fP PP film, in addition to requiring the anti-blocking agent to have a refractive index between 1.49 and 1.50, it should also have one or more of the following characteristics: 1. Anti-blocking The diameter of the primary particles of the agent is less than 0.4 microns; 2 The secondary particles formed by the aggregation of the primary particles of the anti-blocking agent are linear chain structures; 3. The diameter of most secondary particles is less than the visible light wavelength (0.4-0.7 microns); 4 · The tertiary particles formed by the aggregation of these secondary particles are similar to the natural sponge, that is, there should be many gaps between the tertiary particles. The inventor also believes that to further increase the glass transparency of the film, on the one hand, the primary particles should have a round and smooth appearance, that is, the surface does not have sharp edges; on the other hand, migrating chemicals resist the surface of the adhesive. Pre-coating can enhance the anti-blocking function of the product. Based on the above theory, after doing a lot of screening and experiments, we found that a special zeolite named EXP5700-1 produced and sold by German DegussaAG company can meet the above requirements. EXP 5 7 00-1 is an especially good anti-blocking agent in the production of PE and PP films. It can not only guarantee the transparency of the δ-density film, but also many other advantages. Like other zeolites, EXP5700-1 has a refractive index of 1.50 (see Plastics Additives Handbook, Ed. Hans Zweifel, 5th Edition, Munich: Hanser, 2000 "Plastic Additives Handbook", edited by Hans Zweifel, fifth edition, Munich: Lufthansa, 2000, p. 588). -10- 200521203 (8)
Me' 土金 所示 沸石是晶體狀水合鋁矽酸鹽，它的一般化學式爲 /n[(Si02)x(A102)y] * ζΗ20。其中，Me 是鹼金屬或鹼 屬陽離子。EXP 5 7 00 - 1的物理化學數據分析如下表1 200521203 (9) 表1 性狀和檢驗方法 單位 結果 比表面積（N2) 面積測量儀（依據國際標準化組織 ISO 5 7 94-1，Annex D) m2/g 85 平均粒度 多用分粒機，1 〇 〇 μη毛細管（依據美國材料 試驗標準學會ASTM C690- 1 992) μ m 5 烘乾損失 保持1 05 °C 2小時（依據國際標準化組織 ISO 7 8 7-2) % 6 pH値 5 %放入水中（依據國際標準化組織 ISO 7 8 7- 9) 轉 10.1 酸二丁脂D B P吸收値 基於烘乾物質（依據德國工業標準 DIN 53601) g/1〇〇g 200 篩餘物4 5 μ m 噴灑（依據國際標準化組織ISO 3 2 62- 1 9) % 0.05 二氧化矽Si02含量 基於燃燒物質（依據國際標準化組織 ISO 3262-19) % 82 當作N a 2 0的鈉N a含量 基於燃燒物質（依據國際標準化組織 ISO 3 2 62 - 1 8) % 8 當作A ] 2 0 3的鋁A 1含量 基於燃燒物質（依據國際標準化組織 ISO 3262-18) % 9.5 亮度系數Y 依據德國工業標準DIN 53163 - 97 200521203 (10) 參見圖13，它展示了依據本發明製造的 PE膜材60 倍放大圖。生產中，這種PE膜材加入了 0.5 wt.%經遷 移型添加劑（芥酸醯胺）表面處理的EXP 5 7 0 0 - 1母料。 該母料包含了 10 wt·%的EXP 5 7 0 0 -1作爲抗粘連劑。本 圖片是在水平光照射下通過顯微鏡拍攝的。可以看到大量 的抗粘連劑微粒突出在膜材表面上；它因此變得粗糙。比 較而言，圖1 4雖然也是在水平光照射下通過顯微鏡拍攝 的PE膜材60倍放大圖，但生產中它加入的是0.5 wt. %合 成二氧化砂抗粘連劑母料，該母料含1 0 w t · %的合成二氧 化矽，而並沒有依據本發明製造。該膜材表面上的突出微 粒明顯少得多，表面也沒那麼粗糙。 圖15和圖17分別是EXP5 700- 1抗粘連劑微粒的 1，〇〇〇倍、5,00 0倍和1 0,000倍顯微鏡電子掃描圖片。圖 中淸晰地顯示出初級粒子的直徑小於0.4微米；以及初級 粒子聚集形成線性鏈狀結構的次級粒子。大多數線性鏈狀 形態的次級粒子的直徑都小於可見光波長（0.4-0.7微米 )。有部分次級粒子聚集成塊狀，但它們的直徑也都小於 可見光波長（0.4-0.7微米）。次級粒子凝聚成類似天然 海綿的三級粒子，其直徑保持在微米範圍內。這些所形成 的塊狀結構處於聚集體和球團結構之間。另外，我們能看 到三級粒子呈類似天然海綿的結構，粒子之間有許多空隙 。特別地，我們能看到EXP 5 7 00- 1的三級粒子的形態同 天然海綿形態非常相似，如圖2 4所示。初級粒子的形態 圓而光滑，沒有銳角。當可見光穿過球團狀天然海綿結構 -13- 200521203 (11) 的空隙時，光線不是被折射到各個方向而是繼續保持原始 光的強度。初級粒子圓而光滑的邊緣也會減少在被機器加 工時的磨擦，因爲圓而光滑的粒子沒有銳角、不會劃傷設 備之金屬表面。 再者，眾所周知，即使粒子表面已經經過濕潤劑處理 或者偶聯劑處理，在塑料中加入外形光滑的無機粒子會降 低抗拉強度和斷裂伸長度。但是，在塑料中加入這種類似 天然海綿結構的粒子，尤其是因爲類似天然海綿結構的粒 子有齒狀表面和其表面上之裂縫，環繞它們的塑料樹脂就 能“咬住”粒子表面。需要更高的能量級才能把環繞的塑料 和抗粘連劑分開。因此，塑料抗拉強度和斷裂伸長度都不 會降得那麼多。 圖18至圖20分別展示了 Degussa AG公司推出的 Sipernat®900 抗粘連劑粒子 150 0 0 倍、5,000 倍和 10,000 倍的放大圖。可以看出，雖然該抗粘連劑的初級粒子聚集 形成次級粒子，但大多數次級粒子的直徑都大於可見光波 長（〇·4-〇·7微米）。此外，雖然一些次級粒子是線性鏈 狀結構，但他們畢竟佔少數。吹膜實驗證明，如果次級聚 集粒子的線性鏈狀直徑大於可見光的波長，或者如果大多 數次級粒子都不是線性鏈狀結構，但是有一定比例的塊狀 次級粒子，那麼即使初級粒子和沸石有相同的化學結構， 且即使初級粒子有圓而光滑的外形，使用這樣的三級粒子 作爲抗粘連劑還是不能獲得高透明度的ΡΕ或ΡΡ膜材。 圖18至圖20展示了 Sip ernat® 9 00抗粘連劑的次級粒子 -14- 200521203 (12) 雖也是聚集型線性鏈狀結構，但其直徑大於0.4-0.7微米 。如果把這種抗粘連劑加入PE膜材，雖然產品霧度比使 用二氧化矽抗粘連劑的要小，但膜材還是不能達到玻璃透 明度的效果。 圖21展示了 1，〇〇〇瓦鹵鎢燈強光照射下〇·〇2毫米厚 的ΡΕ膜材。根據本發明，這種ρε膜材加入了 2wt·%玻璃 透明度抗粘連劑母料。該母料包含了 l〇wt.%的玻璃透明 度天然海綿狀無機微粒型抗粘連劑（如E X P 5 7 0 0 - 1 )。人 眼不能淸楚地看到抗粘連劑微粒。膜材具有非常高的透明 度。 圖22展示了 1，〇〇〇瓦鹵鎢燈強光照射下〇.〇2毫米厚 的另一種PE膜材。這種PE膜材加入了 2 wt· %沸石抗粘 連劑母料（即Degussa AG公司的Sipernat®9〇〇)。該母 料包含了 1 〇 wt · %的沸石抗粘連劑。人眼能淸楚看到抗 粘連劑微粒導致的明顯霧度。 圖23展示了 1，000瓦鹵燈強光照射下〇.〇2毫米厚的 又一種P E膜材。該膜材加入了 2 wt. %人工合成二_化矽 抗粘連劑母料（即比利時公司 A. Schulmaii生產的105E )。該母料包含了 1〇 wt.%高質量的合成二氧化矽。同樣 ’人眼能淸楚看到抗粘連劑微粒。 圖2 5是在熒光燈照射下、依據本發明而生產的一張 PP梯狀模塑基片。靠近圖片上端的模塑基片厚1毫米， 靠近下端的厚2毫米。該PP模塑基片加入了 2 wt. %的抗 粘連劑母料。該母料含]Owt.% EXP 5 7 00-1的抗粘連劑。 -15- 200521203 (13) 芥酸醯胺這種遷移型添加劑已經被預塗在抗粘連劑上。可 以發現，在熒光燈透射下人眼看不到抗粘連劑粒子。特別 地，該基片垂直方向上如水般透明。圖26是採用顯微鏡 明視場/暗視場光線技術拍攝的，展示了圖2 5中 P P基 片的表面放大圖。可以看到，大量的抗粘連劑遷移到注射 模塑PP基片表面。 爲了生產玻璃透明度高效率低磨耗的抗粘連劑母料， 首先要用高速葉片式硏磨機（如 Henschel攪拌器）把 EXP 5 7 0 0- 1的微粒碾碎。爲了讓膜材表面上有更多的粒子 突出，建議使用遷移型塗層劑，如醯胺蠟，也可以用芥酸 醯胺。比例可以是5份或者5份以上的遷移型添加劑配上 述抗粘連劑的每1 00份。塗層既可使用高速葉片式硏磨機 也可使用螺旋帶式混合機。塗層時，溫度要求在 4 0 °C - 7 0 °C 之間，此時醯胺蠟變軟。 常規的雙螺杆擠出機可以用來製造這種抗粘連劑母料 ’但一些高剪切力單螺杆擠出機（如美國HPM公司製造 的雙波紋單螺杆擠出機）也可以使用。不同等級的低分子 量聚乙烯（聚乙烯P E蠟）可以用作製造母料的分散助劑 。不同等級的低分子量聚丙烯（聚丙烯PP蠟）可以用來 製造P P膜材的抗粘連劑母料。 抗粘連劑母料加入1 〇wt·%的無機微粒型抗粘連劑， 迫已經被廣泛採用。但是，如果只加入5 w t · %的無機微 粒型抗粘連劑，也是可以的。組合了有機抗粘連劑（如油 醒胺或者芥酸醯胺等）的母料配方也是可行的。 -16- 200521203 (14) 作爲選擇，在聚合過程中，把EXP57()(K;l組成的抗 粘連劑直接加入PE和PP樹脂，即在聚合過程的製粒環 節加入。因爲大多數聚合生產廠家在製粒環節都使用大型 雙螺擠出機，而且這種大型雙螺擠出機的剪切力都很大， 所以可以在聚合過程的製粒環節把玻璃透明度天然海綿狀 無機微粒型ί几粘連劑直接加入p E和p p樹脂。彳日是，把 乾末狀添加劑在製粒環節加入ρ Ε和ρ ρ樹脂可以採取不 同的方法，例如，先製造添加劑懸浮液體，再用液體泵注 射到製粒雙螺杆擠出機中；或者先製造添加劑母料，再把 母料通過重量計量進料器加入製粒雙螺杆擠出機。有的情 況下’也可以把抗粘連劑粉末直接加入大型製粒雙螺杆濟 出機。所得到的樹脂中抗粘連劑的含量可爲〇 . 〇 2 wt. % (亦 即 200ρρηι)至 0.5wt.%(亦即 5,000ppm)。 需要指出的是，以上闡述只是說明和描述本發明具體 實施的一些範例；在遵守以下要求規定的發明範圍的基礎 上’可以進行調整和/或變更。 以下錯者梦考附圖及照片詳述本發明的具體實例（僅 用以舉例說明），其中： 【圖式簡單說明】 圖1是塑料薄膜生產示意圖 圖2是粘附現象示意圖 圖3展示了微粒型抗粘連劑的工作原理 圖4是圖3中圈畫部分的放大圖 -17- 200521203 (15) 圖5是遷移型抗粘連劑的工作原理 圖6展示了光線穿過含有抗粘連劑的薄膜時的途徑 圖7是圖6中圈畫部分的放大圖 圖8展示了含有抗粘連劑的熔融材料通過機器基板表 面時的情景 圖9展示了由化學引力聚集起來的初級粒子結構 Η 10 展示了由物理引力凝聚起來的初級粒子結 構 圖1 1 是放大1,000倍的天然矽石，摘自《塑料添 加劑手冊》，H a n s Z w e i f e 1編，第五版，慕尼黑：漢莎， 2,000 圖12 是放大1 000倍的人工合成二氧化矽，摘自 《塑料添加劑手冊》，Hans zweifel編，第五版，慕尼黑 :漢莎，2,〇00The zeolite shown by Me 'soil gold is a crystalline hydrated aluminosilicate. Its general chemical formula is / n [(Si02) x (A102) y] * ζΗ20. Among them, Me is an alkali metal or a basic cation. The analysis of the physical and chemical data of EXP 5 7 00-1 is shown in Table 1 200521203 (9) Table 1 Properties and test methods Unit results Specific surface area (N2) Area measuring instrument (according to ISO 5 7 94-1, Annex D) m2 / g 85 Multi-purpose particle sizer with average particle size, 100 μη capillary (according to ASTM C690-1992) μ m 5 Drying loss maintained at 1 05 ° C for 2 hours (according to ISO 7 8 7 -2)% 6 pH 5% 5% into water (according to ISO 7 8 7-9) to 10.1 Dibutyl acid DBP absorption based on drying material (according to German industrial standard DIN 53601) g / 1〇〇 g 200 sieve residue 4 5 μm Spraying (according to ISO 3 2 62- 1 9)% 0.05 Silicon dioxide Si02 content based on combustible substances (according to ISO 3262-19)% 82 as N a 2 Sodium Na content of 0 is based on flammable substance (according to ISO 3 2 62-1 8)% 8 is regarded as A] 2 0 3 Aluminum A 1 content is based on flammable substance (according to ISO 3262-18)% 9.5 Brightness Y according to German Industrial Standard DIN 5 3163-97 200521203 (10) Refer to FIG. 13, which shows a 60-times enlarged view of a PE film material manufactured according to the present invention. In production, this PE film was added with a 0.5 wt.% EXP 5 7 0 0-1 masterbatch surface-treated with a migration additive (ammonium erucate). The masterbatch contains 10 wt ·% of EXP 5 7 0 0 -1 as an anti-blocking agent. This picture was taken with a microscope under horizontal light. It can be seen that a large amount of anti-adhesive particles protrude on the surface of the film; it therefore becomes rough. In comparison, although Figure 14 is also a 60-times magnified view of a PE film material taken by a microscope under horizontal light irradiation, it adds 0.5 wt.% Synthetic sand anti-blocking agent masterbatch in production. The masterbatch Contains 10 wt.% Synthetic silicon dioxide, which is not manufactured according to the present invention. The number of protruding particles on the surface of the film is significantly less, and the surface is not so rough. Figures 15 and 17 are 1, 000, 5,000, and 10,000 times electron micrographs of EXP5 700-1 anti-adhesive particles, respectively. The figure clearly shows that the diameter of the primary particles is less than 0.4 micrometers; and the secondary particles where the primary particles aggregate to form a linear chain structure. Most linear chain-shaped secondary particles have a diameter smaller than the wavelength of visible light (0.4-0.7 microns). Some secondary particles are aggregated into blocks, but their diameters are also smaller than the visible light wavelength (0.4-0.7 microns). Secondary particles condense into tertiary particles that resemble natural sponges, with diameters kept in the micrometer range. These formed massive structures are located between aggregates and pellets. In addition, we can see that the tertiary particles have a structure similar to a natural sponge, with many gaps between the particles. In particular, we can see that the morphology of the tertiary particles of EXP 5 7 00-1 is very similar to that of natural sponges, as shown in Figure 24. The morphology of the primary particles is round and smooth with no acute angles. When visible light passes through the voids of the pellet-like natural sponge structure -13- 200521203 (11), the light is not refracted in all directions but continues to maintain the intensity of the original light. The round and smooth edges of the primary particles will also reduce friction during processing by the machine, because the round and smooth particles have no sharp angles and will not scratch the metal surface of the device. Furthermore, it is well known that even if the surface of the particles has been treated with a wetting agent or a coupling agent, the addition of smooth inorganic particles to the plastic will reduce the tensile strength and elongation at break. However, the inclusion of such natural sponge-like particles in plastics, especially because the particles similar to the natural sponge structure have toothed surfaces and cracks on their surfaces, the plastic resin surrounding them can "bit" the particle surface. Higher energy levels are needed to separate the surrounding plastic from the anti-blocking agent. Therefore, neither the tensile strength nor the elongation at break of the plastic will be reduced so much. Figures 18 to 20 show magnified views of Sipernat® 900 anti-blocking agent particles from Degussa AG at 150,000, 5,000, and 10,000 times, respectively. It can be seen that although the primary particles of the anti-blocking agent aggregate to form secondary particles, the diameter of most secondary particles is larger than the visible light wavelength (0.4-0.7 microns). In addition, although some secondary particles have a linear chain structure, they are in the minority after all. Film blowing experiments prove that if the linear chain diameter of the secondary aggregate particles is larger than the wavelength of visible light, or if most secondary particles are not linear chain structures, but there are a certain proportion of block secondary particles, then even if the primary particles and Zeolite has the same chemical structure, and even if the primary particles have a round and smooth appearance, using such tertiary particles as an anti-blocking agent still cannot obtain a highly transparent PE or PP film. Figures 18 to 20 show the secondary particles of Sip ernat® 9 00 antiblocking agent. -14- 200521203 (12) Although it is an aggregate linear chain structure, its diameter is greater than 0.4-0.7 microns. If this anti-blocking agent is added to the PE film material, although the product haze is smaller than that using the silica anti-blocking agent, the film material still cannot achieve the effect of glass transparency. Figure 21 shows a PE film with a thickness of 0.02 mm under the strong light of a 1,000-watt tungsten halogen lamp. According to the present invention, this ρε film is added with a 2wt.% Glass transparency anti-blocking agent master batch. The masterbatch contains 10 wt.% Glass transparent natural sponge-like inorganic particulate anti-blocking agent (such as E X P 5 7 0-1). The human eye cannot see the anti-adhesive particles clearly. The film has very high transparency. Fig. 22 shows another PE film having a thickness of 0.02 mm under the strong light of a 10,000-watt tungsten halogen lamp. This PE film was added with a 2 wt.% Zeolite anti-blocking agent master batch (ie Sipernat® 900 from Degussa AG). The masterbatch contains 10 wt.% Zeolite anti-blocking agent. The human eye can clearly see the obvious haze caused by the anti-adhesive particles. Figure 23 shows another PE film having a thickness of 0.02 mm under the strong light of a 1,000 watt halogen lamp. The film was added with 2 wt.% Artificially synthesized di-silicone anti-blocking agent masterbatch (ie 105E produced by the Belgian company A. Schulmaii). The masterbatch contains 10 wt.% High-quality synthetic silica. Similarly, the human eye can see the anti-adhesive particles. Fig. 25 is a PP ladder-shaped molded substrate produced according to the present invention under the illumination of a fluorescent lamp. The molded substrate near the upper end of the picture is 1 mm thick and 2 mm near the lower end. The PP molding substrate was added with 2 wt.% Anti-blocking agent masterbatch. The masterbatch contains an anti-blocking agent of Owt.% EXP 5 7 00-1. -15- 200521203 (13) Erbium erucate, a migration additive, has been pre-coated on anti-blocking agents. It was found that the anti-adhesive particles were not visible to the human eye under the transmission of a fluorescent lamp. In particular, the substrate is transparent like water in the vertical direction. Figure 26 was taken using the microscope bright-field / dark-field light technology, showing an enlarged view of the surface of the PP substrate in Figure 25. It can be seen that a large amount of the anti-blocking agent migrates to the surface of the injection-molded PP substrate. In order to produce anti-blocking agent masterbatch with high transparency and high efficiency, the first step is to use a high-speed blade honing machine (such as a Henschel mixer) to crush the particles of EXP 5 7 0-1. In order to make more particles protrude on the surface of the film, it is recommended to use a migration coating agent, such as ammonium wax, or ammonium erucate. The proportion may be 5 parts or more per 100 parts of the migration additive combined with the anti-blocking agent. The coating can be applied using either a high speed blade honing machine or a spiral belt mixer. When coating, the temperature should be between 40 ° C-70 ° C. At this time, the ammonium wax becomes soft. Conventional twin-screw extruders can be used to make this anti-blocking agent masterbatch ', but some high-shear single-screw extruders (such as twin-corrugated single-screw extruders manufactured by HPM, USA) can also be used. Different grades of low molecular weight polyethylene (polyethylene PE wax) can be used as dispersion aids in the manufacture of masterbatches. Different grades of low molecular weight polypropylene (polypropylene PP wax) can be used to make anti-blocking agent master batches for PP film. The anti-blocking agent masterbatch is added with 10 wt.% Inorganic particulate anti-blocking agent, which has been widely used. However, it is also possible to add only 5 w t ·% of the inorganic particulate anti-blocking agent. Masterbatch formulations combining organic anti-blocking agents such as acetamide or erucamide are also possible. -16- 200521203 (14) As an option, in the polymerization process, an anti-blocking agent composed of EXP57 () (K; l) is directly added to the PE and PP resins, that is, it is added during the granulation step of the polymerization process. Because most polymerization production Manufacturers use large twin-screw extruders in the granulation process, and the large twin-screw extruders have large shear forces, so they can make glass transparent natural sponge-like inorganic particulates in the granulation process of the polymerization process. Several adhesives are directly added to p E and pp resins. The next day, different methods can be used to add dry powder additives to ρ Ε and ρ ρ resins in the granulation process. For example, the additive suspension liquid is first manufactured and then injected with a liquid pump. Into the granulating twin-screw extruder; or first make the additive master batch, and then add the master batch to the granulating twin-screw extruder through a weight metering feeder. In some cases, it is also possible to add the anti-blocking agent powder directly The large-scale granulated twin-screw extruder. The content of the anti-blocking agent in the obtained resin may be from 0.02 wt.% (That is, 200ρρηι) to 0.5wt.% (That is, 5,000ppm). It should be noted that The above explanation is just Explain and describe some examples of the specific implementation of the present invention; adjustments and / or changes can be made on the basis of complying with the scope of the invention specified in the following requirements. The following mistakes dream of the drawings and photos detail specific examples of the present invention (only for (Illustration), among which: [Schematic description] Figure 1 is a schematic diagram of the production of plastic film Figure 2 is a schematic diagram of the adhesion phenomenon Figure 3 shows the working principle of particulate anti-blocking agent Figure 4 is an enlarged view of the circled part in Figure 3 -17- 200521203 (15) Figure 5 is the working principle of migration type anti-blocking agent Figure 6 shows the way when light passes through the film containing anti-blocking agent Figure 7 is an enlarged view of the circled part in Figure 6 Figure 8 shows A scene of a molten material containing an anti-blocking agent passing through the surface of a machine substrate. Figure 9 shows the structure of primary particles gathered by chemical gravity. 10 shows the structure of primary particles gathered by physical gravity. Figure 1 1 shows 1,000 times natural silicon magnification. Stone, excerpted from the Handbook of Plastic Additives, edited by Hans Z weife, 5th edition, Munich: Lufthansa, 2,000 Silicon, from "Plastics Additives Handbook", Hans zweifel ed., Fifth Edition, Munich: Lufthansa, 2, 〇00
圖1 3 是放大 6 0倍的、根據本發明所製造的 P E 薄膜 圖1 4 是放大6 0倍的、以傳統常用抗粘連劑製造 的PE薄膜 圖丨5 是放大1，000倍的、在生產圖13薄膜中所 添加的抗粘連劑 圖I 6 是放大5，0 0 0倍的、在生產圖1 3薄膜中所 添加的抗粘連劑 圖17 是放大10,000倍的、在生產圖13薄膜中所 添加的抗粘連劑 -18 - 200521203 (16) 圖18 是放大1，000倍的、目前市面上由Degussa AG公司生產的一種抗粘連劑，商標爲SIPERNAT®900 圖1 9 是放大5，0 0 0倍的、如圖1 8所不的商標爲 SIPERNAT®9 0 0的抗粘連齊！1 圖2 0 是放大1 0，0 0 0倍的、如圖1 8所示的商標爲 SIPERNAT®900的抗粘連齊^ 圖2 1 展示了 1 5 0 0 0瓦鹵鎢燈強光照射下、根據本 發明添加了 EXP5 700 - 1抗粘連劑的PE薄膜（厚0.02毫米 ) 圖2 2 展示了 1 5 〇 0 0瓦鹵鎢燈強光照射下、使用了 商標爲SIPERNAT®9 0 0抗粘連劑的PE薄膜（厚0.02毫 米） 圖23 展示了 15〇〇〇瓦鹵燈強光照射下、使用了二 氧化砂抗粘連劑的pE薄膜（厚〇.02毫米） 圖2 4 展不了天然海綿 圖2 5 展示了熒光燈照射下、根據本發明所製造 的一種透明P P梯狀模塑基片 圖26 展示了圖25中PP基片的表面放大圖。 -19-Figure 13 is a PE film made according to the present invention at a magnification of 60 times. Figure 14 is a PE film made with a conventional anti-blocking agent at a magnification of 60 times. Figure 5 is a magnification of 1,000 times at The anti-blocking agent added in the production of the film of FIG. 13 is shown in FIG. 6 which is an enlarged 5,000 times. The anti-blocking agent added in the production of the film of FIG. 13 is shown in FIG. Anti-blocking agent-18 added in 2005-200521203 (16) Figure 18 is a kind of anti-blocking agent produced by Degussa AG company on the market at a magnification of 1,000 times. The trademark is SIPERNAT® 900. Figure 1 9 is a magnification 5, 0 0 0 times the anti-blocking mark of SIPERNAT® 9 0 0 as shown in Figure 18! 1 Figure 2 0 is an anti-blocking product with SIPERNAT®900 trademark as shown in Figure 18 with a magnification of 10,0 0 × ^^ Figure 2 1 shows a 15 0 0 Watt halogen lamp under strong light 2. PE film with EXP5 700-1 anti-blocking agent added according to the present invention (0.02 mm thick) Figure 2 2 shows a 15 000 watt tungsten halogen lamp under strong light, using the trademark SIPERNAT® 9 0 0 Adhesive PE film (thickness 0.02 mm) Figure 23 shows pE film (thickness 0.02 mm) using sand dioxide anti-blocking agent under strong light from a 15,000 watt halogen lamp. Figure 2 4 Sponge FIG. 25 shows a transparent PP ladder-shaped molding substrate manufactured according to the present invention under the illumination of a fluorescent lamp. FIG. 26 shows an enlarged view of the surface of the PP substrate in FIG. 25. -19-